JPH03123776A - Production of 2-furancarboxylic acid - Google Patents
Production of 2-furancarboxylic acidInfo
- Publication number
- JPH03123776A JPH03123776A JP26172089A JP26172089A JPH03123776A JP H03123776 A JPH03123776 A JP H03123776A JP 26172089 A JP26172089 A JP 26172089A JP 26172089 A JP26172089 A JP 26172089A JP H03123776 A JPH03123776 A JP H03123776A
- Authority
- JP
- Japan
- Prior art keywords
- furfural
- furancarboxylic acid
- reaction
- hydrogen peroxide
- ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 16
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 22
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 11
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 239000000575 pesticide Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- KDCGOANMDULRCW-UHFFFAOYSA-N 7H-purine Chemical compound N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 sodium hydroxide Chemical class 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、２−フランカルボン酸の製造方法に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing 2-furancarboxylic acid.
２−フランカルボン酸は、常温では板状の結晶性で、融
点１３３〜１３４℃の昇華性を有する化合物であり、一
般に医薬品中間体、香料、農薬、樹脂等の原料として、
また、その誘導体も様々な用途に使用されている有用な
物質である。2-Furancarboxylic acid is a compound that is plate-like crystalline at room temperature and has sublimation properties with a melting point of 133 to 134°C, and is generally used as a raw material for pharmaceutical intermediates, fragrances, agricultural chemicals, resins, etc.
Further, its derivatives are also useful substances used for various purposes.
（従来の技術）
従来、２−フランカルボン酸の製造方法としては、
■銀、白金、パラジウム等の金属酸化物触媒の存在下に
水酸化ナトリウム等の水酸化アルカリとフルフラールを
併行して滴下し、酸素または空気により酸化する方法（
Ｏｒｇａｎｉｃｓｙｎｔｈｅｓｉｓ ｃｏ、Ｉｔ
Ｖａｔ、４ｐ４８３〜４８６）、
■水酸化アルカリとフルフラールとを併行滴下し、次亜
塩素酸ナトリウムを酸化剤として用いる方法（特公昭２
５−１１３０号）、
■カニツアーロ反応による方法（Ｏｒｇａｎｉｃｓｙｎ
ｔｈｅｓｉｓ ｃｏ、ＩＩ Ｖｏｌ、１ｐ２７６〜
２８０）
等が知られている。(Prior art) Conventionally, methods for producing 2-furancarboxylic acid include: ■ Dropwise addition of an alkali hydroxide such as sodium hydroxide and furfural in parallel in the presence of a metal oxide catalyst such as silver, platinum, or palladium. , a method of oxidizing with oxygen or air (
Organicsynthesis co, It
Vat, 4p483-486), ■Method of simultaneously dropping alkali hydroxide and furfural and using sodium hypochlorite as an oxidizing agent (Special Publications Showa 2)
5-1130), ■Cannitzaro reaction method (Organicsyn
thesis co, II Vol, 1p276~
280) etc. are known.
（発明が解決しようとする課題）
しかしながら、これらの従来の製造方法では、必ず水酸
化ナトリウム等の水酸化アルカリの存在下に反応が行わ
れるため、副反応としてカニツアーロ反応が進み過ぎて
２−フランカルボン酸以外にフルフリルアルコールが副
生する。(Problems to be Solved by the Invention) However, in these conventional production methods, the reaction is always carried out in the presence of an alkali hydroxide such as sodium hydroxide, so the cannizarro reaction proceeds too much as a side reaction, resulting in the production of 2-furan. In addition to carboxylic acid, furfuryl alcohol is produced as a by-product.
また、工業的に行う場合も、触媒回収や装置腐食等の点
で問題がある。Furthermore, when carried out industrially, there are problems in terms of catalyst recovery, equipment corrosion, etc.
さらに、ピリジン溶媒下常温でフルフラールと過酸化水
素を反応させて、２−フランカルボン酸を製造する方法
（特公昭３４−６１１３号）が知られているが、反応速
度が著しく遅いという欠点がある。Furthermore, a method for producing 2-furancarboxylic acid by reacting furfural with hydrogen peroxide in a pyridine solvent at room temperature is known (Japanese Patent Publication No. 34-6113), but it has the drawback that the reaction rate is extremely slow. .
上記の問題を解決するという本発明の目的は、以下に示
す方法により達成される。The object of the present invention to solve the above problem is achieved by the method shown below.
本発明者の研究によれば、環内に少なくとも一つ以上の
窒素原子を含む芳香族性をもつ複素環式化合物の存在下
、フルフラールを過酸化水素で酸化して、２−フランカ
ルボン酸を製造するに際し、反応温度５０〜１００℃で
反応を行うことにより、従来のピリジンを用いた室温で
の反応より、はるかに高活性で２−フランカルボン酸が
得られることが見いだされた。According to the research of the present inventor, furfural is oxidized with hydrogen peroxide in the presence of an aromatic heterocyclic compound containing at least one nitrogen atom in the ring to produce 2-furancarboxylic acid. It has been found that 2-furancarboxylic acid can be obtained with much higher activity by carrying out the reaction at a reaction temperature of 50 to 100° C. than in the conventional reaction at room temperature using pyridine.
（発明の構成）
即ち、本発明は
「環内に少なくとも一つ以上の窒素原子を含む芳香族性
を有する複素環式化合物の存在下、反応温度５０〜１０
０℃において、フルフラールを過酸化水素で酸化するこ
とを特徴とする２−フランカルボン酸の製造方法」
である。(Structure of the Invention) That is, the present invention provides ``in the presence of an aromatic heterocyclic compound containing at least one nitrogen atom in the ring, a reaction temperature of 50 to 10
A method for producing 2-furancarboxylic acid, which comprises oxidizing furfural with hydrogen peroxide at 0°C.
以下に本発明の２−フランカルボン酸の製造方法を詳細
に説明する。The method for producing 2-furancarboxylic acid of the present invention will be explained in detail below.
フルフラールを酸化して２−フランカルボン酸を製造す
る際の化学反応式は以下のように表わされる。The chemical reaction formula for producing 2-furancarboxylic acid by oxidizing furfural is expressed as follows.
また、上記反応をフルフラール１モルに対して、環内に
少なくとも一つ以上の窒素原子を含む芳香族性をもつ複
素環式化合物１〜３モル倍を添加して行う場合は、２−
フランカルボン酸への選択性も従来（特公昭３４−６１
１３号）の反応条件での反応より向上することが見いだ
された。In addition, when the above reaction is carried out by adding 1 to 3 moles of an aromatic heterocyclic compound containing at least one nitrogen atom in the ring to 1 mole of furfural, 2-
The selectivity to furancarboxylic acid was also conventional
It was found that the reaction was improved over the reaction conditions of No. 13).
本発明で使用し得る環内に少なくとも一つ以上の窒素原
子を含む芳香族性をもつ複素環式化合物としては以下の
ような化合物がある。Examples of aromatic heterocyclic compounds containing at least one nitrogen atom in the ring that can be used in the present invention include the following compounds.
ピリジン、ピリミジン、プリン、キノリン、イソキノリ
ン、カルバゾール、ピロール、イミダゾール、オキサゾ
ール、チアゾール、ピラゾール等が使用でき、これらは
メチル、エチル、プロピル等のアルキル基や、フルオロ
、クロロ、ブロモ等のハロゲン基や、アミノ基、ニトロ
基等の置換基を有していてもよい。Pyridine, pyrimidine, purine, quinoline, isoquinoline, carbazole, pyrrole, imidazole, oxazole, thiazole, pyrazole, etc. can be used, and these include alkyl groups such as methyl, ethyl, propyl, halogen groups such as fluoro, chloro, bromo, etc. It may have a substituent such as an amino group or a nitro group.
中でも、ピリジンおよびその誘導体が好ましい。Among these, pyridine and its derivatives are preferred.
本発明では、環内に少なくとも一つ以上の窒素原子を含
む芳香族性をもつ複素環式化合物は、フルフラール１モ
ルに対して、１〜３モル倍、好ましくは１．５〜２．０
モル倍用いる。In the present invention, the aromatic heterocyclic compound containing at least one nitrogen atom in the ring is 1 to 3 times, preferably 1.5 to 2.0 times, per mole of furfural.
Use twice the mole.
環内に少なくとも一つ以上の窒素原子を含む芳香族性を
もつ複素環式化合物がフルフラール１モルに対して、１
モル未満の場合には、反応系内の酸性度が強くなり、フ
ラン環の開環等が起こり、フルフラールの２−フランカ
ルボン酸への選択性が著しく低下する。An aromatic heterocyclic compound containing at least one nitrogen atom in the ring is 1 mole of furfural.
When the amount is less than mol, the acidity in the reaction system becomes strong, ring opening of the furan ring, etc. occurs, and the selectivity of furfural to 2-furancarboxylic acid decreases significantly.
逆に、３モル倍以上の場合には、反応系内のフルフラー
ルや過酸化水素濃度低下の影響が出てきて、フルフラー
ルの２−フランカルボン酸への転化率が低下してくる。On the other hand, when the amount is 3 times or more by mole, the concentration of furfural and hydrogen peroxide in the reaction system decreases, resulting in a decrease in the conversion rate of furfural to 2-furancarboxylic acid.
本発明では、反応に用いる過酸化水素は、フルフラール
１モルに対して、１モル倍以上用いることが望ましいが
、大過剰に用いると、精製時に未反応の過酸化水素の処
理が必要となり、必然的にコストアップにつながる。In the present invention, hydrogen peroxide used in the reaction is desirably used at least 1 mole times per mole of furfural, but if used in large excess, unreacted hydrogen peroxide will need to be treated during purification, resulting in unavoidable This leads to an increase in costs.
したがって、好ましくは、フルフラール１モルに対して
１モル以上、２モル倍以下で用いる。Therefore, it is preferably used in an amount of 1 mole or more and 2 moles or less per mole of furfural.
また、過酸化水素の濃度は少なくとも３５Ｗ／Ｗ％以上
で用いるのが好ましい。Further, it is preferable that the concentration of hydrogen peroxide is at least 35 W/W% or more.
３５Ｗ／Ｗ％未満だと上記のモル比率で使用するには使
用体積が大となり大きな反応装置を必要とする。If it is less than 35 W/W%, the volume used will be large and a large reactor will be required to use it at the above molar ratio.
また、反応速度も遅くなるので好ましくない。Further, the reaction rate becomes slow, which is not preferable.
反応は、公知の方法のようにバッチ張り込みで行っても
進行するが、工業的に実施する場合の除熱の問題等を考
慮すると、環内に少なくとも一つ以上の窒素原子を含む
芳香族性をもつ複素環式化合物を反応器に張り込みフル
フラールと過酸化水素を逐次仕込んで行く方法または、
環内に少なくとも一つ以上の窒素原子を含む芳香族性を
もつ複素環式化合物とフルフラールを反応器に張り込み
、過酸化水素を逐次仕込んで行く方法のどちらかで行う
のが好ましい。The reaction proceeds even if it is carried out in a batch manner as in a known method, but considering the problem of heat removal in industrial implementation, aromatic compounds containing at least one nitrogen atom in the ring A method of filling a reactor with a heterocyclic compound having
It is preferable to carry out the reaction by charging an aromatic heterocyclic compound containing at least one nitrogen atom in the ring and furfural into a reactor, and then sequentially charging hydrogen peroxide.
反応温度は、通常５０〜１００℃程度、好ましくは６０
〜８０℃程度とするのがよい。The reaction temperature is usually about 50 to 100°C, preferably 60°C.
The temperature is preferably about 80°C.
５０℃未満となるとフルフラールの２−フランカルボン
酸への転化率が著しく低くなり、逆に１００℃を越える
とフルフラールおよび過酸化水素の２−フランカルボン
酸への選択性は著しく低くなり、環内に少なくとも一つ
以上の窒素原子を含む芳香族性をもつ複素環式化合物の
酸化速度も速くなるので好ましくない。When the temperature is below 50℃, the conversion rate of furfural to 2-furancarboxylic acid becomes extremely low.On the other hand, when the temperature exceeds 100℃, the selectivity of furfural and hydrogen peroxide to 2-furancarboxylic acid becomes extremely low, and This is not preferable because the oxidation rate of aromatic heterocyclic compounds containing at least one nitrogen atom becomes faster.
また、反応時間は環内に少なくとも一つ以上の窒素原子
を含む芳香族性をもつ複素環式化合物の使用量、過酸化
水素濃度、反応温度に応じて適宜選択すればよいが、通
常３〜１０時間程度、好ましくは４〜６時間程度とすれ
ばよい。The reaction time may be appropriately selected depending on the amount of the aromatic heterocyclic compound containing at least one nitrogen atom in the ring, the hydrogen peroxide concentration, and the reaction temperature; The duration may be about 10 hours, preferably about 4 to 6 hours.
反応終了後、公知の方法に準じて、例えば、得られた反
応粗液を塩酸、硫酸等で処理して２−フランカルボン酸
を析出させ、次いで濾過することにより高純度の結晶を
得ることができる。After the reaction is completed, high-purity crystals can be obtained by treating the obtained reaction crude liquid with hydrochloric acid, sulfuric acid, etc. to precipitate 2-furancarboxylic acid, and then filtering it according to a known method. can.
本発明の２−フランカルボン酸の製造方法における具体
的な実施態様としては以下のようなものがある。Specific embodiments of the method for producing 2-furancarboxylic acid of the present invention include the following.
（ａ）フルフラール１モルに対して環内に少なくとも一
つ以上の窒素原子を含む芳香族性をもつ複素環式化合物
１〜３モル倍添加することを特徴とする特許請求の範囲
記載の製造方法。(a) The manufacturing method according to the claims, characterized in that 1 to 3 moles of an aromatic heterocyclic compound containing at least one nitrogen atom in the ring is added to 1 mole of furfural. .
（ｂ）環内に少なくとも一つ以上の窒素原子を含む芳香
族性をもつ複素環式化合物がピリジンである特許請求の
範囲記載の製造方法。(b) The manufacturing method according to the claims, wherein the aromatic heterocyclic compound containing at least one nitrogen atom in the ring is pyridine.
（ｅ）環内に少なくとも一つ以上の窒素原子を含む芳香
族性をもつ複素環式化合物がピリジンである特許請求の
範囲記載の製造方法。(e) The manufacturing method according to the claims, wherein the aromatic heterocyclic compound containing at least one nitrogen atom in the ring is pyridine.
（発明の効果）
本発明によれば、環内に少なくとも一つ以上の窒素原子
を含む芳香族性をもつ複素環式化合物の存在下フルフラ
ールから２−フランカルボン酸を高活性、高選択性で収
得できる製造方法が提供される。(Effects of the Invention) According to the present invention, 2-furancarboxylic acid is produced from furfural with high activity and high selectivity in the presence of an aromatic heterocyclic compound containing at least one nitrogen atom in the ring. A method of manufacturing is provided.
（実施例）
以下に実施例および比較例を挙げて本発明の詳細な説明
するが、本発明はこれら各側に限定されるものではない
。(Examples) The present invention will be described in detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these.
実施例１
冷却器、撹拌機及び温度計を備えた１００ｍＮジャケッ
ト付フラスコにフルフラール２０ｇ１３５Ｗ／Ｗ％過酸
化水素水３０ｇ１ピリジン１４ｇを張込み、５０℃で６
時間反応させた。Example 1 A 100 mN jacketed flask equipped with a condenser, a stirrer, and a thermometer was charged with 20 g of furfural, 30 g of 35 W/W% hydrogen peroxide solution, and 14 g of pyridine.
Allowed time to react.
反応終了後、反応粗液に塩酸を加え、２−フランカルボ
ン酸をガスクロマトグラフィーにより分析した結果、２
−フランカルボン酸の収率は４７゜５％で、フルフラー
ルの２−フランカルボン酸選択性は８３．８％であった
。After the reaction was completed, hydrochloric acid was added to the crude reaction solution, and 2-furancarboxylic acid was analyzed by gas chromatography.
The yield of -furancarboxylic acid was 47.5%, and the selectivity of furfural to 2-furancarboxylic acid was 83.8%.
実施例２
７０℃で反応を行った以外、実施例１と同様の操作を行
った。Example 2 The same operation as in Example 1 was performed except that the reaction was carried out at 70°C.
その結果、２−フランカルボン酸の収率は、７７．３％
で、フルフラールの２−フランカルボン酸選択性は、８
６．６％であった。As a result, the yield of 2-furancarboxylic acid was 77.3%.
So, the selectivity of furfural for 2-furancarboxylic acid is 8
It was 6.6%.
比較例１
室温で反応を行った以外、実施例１と同様の操作を行っ
た。その結果、２−フランカルボン酸の収率は、１９．
１％で、フルフラールの２−フランカルボン酸選択性は
５９．３％であった。Comparative Example 1 The same operation as in Example 1 was performed except that the reaction was carried out at room temperature. As a result, the yield of 2-furancarboxylic acid was 19.
At 1%, the selectivity of furfural to 2-furancarboxylic acid was 59.3%.
実施例１．２は特公昭３４−６１１３号公報に開示され
ている条件（比較例１）で反応した場合より著しく収率
がよく、フルフラールの２−フランカルボン酸選択性も
優れていることを示している。In Example 1.2, the yield was significantly better than when the reaction was carried out under the conditions disclosed in Japanese Patent Publication No. 34-6113 (Comparative Example 1), and the selectivity of furfural to 2-furancarboxylic acid was also excellent. It shows.
実施例３
冷却器、撹拌機、温度計及び仕込ポンプ２台を備えた３
００ ｍｌジャケット付フラスコにフルフラール４８
ｇを張り込み、７０℃で３５Ｗ／Ｗ％過酸化水素水２７
ｇにピリジン６０ｇを３時間かけて仕込ながら反応させ
、仕込終了後７０℃でさらに３時間反応させた。Example 3 3 equipped with a cooler, a stirrer, a thermometer and two dosing pumps
Furfural 48 in a 00 ml jacketed flask
g and 35W/W% hydrogen peroxide solution 27 at 70℃.
60 g of pyridine was charged over 3 hours and reacted, and after the completion of the charging, the reaction was further carried out at 70°C for 3 hours.
実施例１と同様に分析した結果、２−プランカルボン酸
の収率は７８．２％でフルフラールの２−フランカルボ
ン酸選択性は８６．８％であった。As a result of analysis in the same manner as in Example 1, the yield of 2-furancarboxylic acid was 78.2%, and the selectivity of furfural to 2-furancarboxylic acid was 86.8%.
比較例２
ピリジン仕込量が２０ｇになった以外、実施例３と同様
の操作を行った。Comparative Example 2 The same operation as in Example 3 was performed except that the amount of pyridine charged was 20 g.
その結果、２−フランカルボン酸の収率は５８゜４％で
フルフラールの２−フランカルボン酸選択性は３８．５
％であった。As a result, the yield of 2-furancarboxylic acid was 58.4%, and the selectivity of furfural to 2-furancarboxylic acid was 38.5.
%Met.
実施例１と比較例２は、フルフラール１モルに対するピ
リジンの量が１モル倍未満であると、著しくフルフラー
ルの２−フランカルボン酸選択性の低下することを示し
ている。Example 1 and Comparative Example 2 show that when the amount of pyridine is less than 1 mole of furfural, the selectivity of furfural to 2-furancarboxylic acid is significantly reduced.
手 続 補 正 書 （自発）平成２年５月１
０日Procedural amendment (voluntary) May 1, 1990
0 days
Claims (1)
を有する複素環式化合物の存在下、反応温度５０〜１０
０℃において、フルフラールを過酸化水素で酸化するこ
とを特徴とする２−フランカルボン酸の製造方法。In the presence of an aromatic heterocyclic compound containing at least one nitrogen atom in the ring, the reaction temperature is 50 to 10
A method for producing 2-furancarboxylic acid, which comprises oxidizing furfural with hydrogen peroxide at 0°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26172089A JPH03123776A (en) | 1989-10-06 | 1989-10-06 | Production of 2-furancarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26172089A JPH03123776A (en) | 1989-10-06 | 1989-10-06 | Production of 2-furancarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03123776A true JPH03123776A (en) | 1991-05-27 |
Family
ID=17365773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26172089A Pending JPH03123776A (en) | 1989-10-06 | 1989-10-06 | Production of 2-furancarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03123776A (en) |
-
1989
- 1989-10-06 JP JP26172089A patent/JPH03123776A/en active Pending
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